CN105895971A - Electrical storage device including anode and cathode - Google Patents
Electrical storage device including anode and cathode Download PDFInfo
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- CN105895971A CN105895971A CN201610011441.0A CN201610011441A CN105895971A CN 105895971 A CN105895971 A CN 105895971A CN 201610011441 A CN201610011441 A CN 201610011441A CN 105895971 A CN105895971 A CN 105895971A
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- Prior art keywords
- charge storage
- electrode collector
- storage element
- oxide
- negative pole
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/604—Polymers containing aliphatic main chain polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
An electrical storage device includes: a conductive anode collector; a conductive cathode collector; an anode between the anode collector and the cathode collector, the anode containing a mixture of an insulating material and an oxide of cerium; and a cathode between the cathode collector and the anode.
Description
Technical field
The present invention relates to charge storage element and manufacture method thereof.
Background technology
In recent years, the most general along with information association equipment, communication equipments etc. such as personal computer, video camera and mobile phones
And, the exploitation of the charge storage element being used as its power supply comes into one's own.It addition, in industrial circles such as automobiles, the most
Carry out the exploitation of the battery of used for electric vehicle or the high output of Hybrid Vehicle and high power capacity.Now, in various batteries,
From the point of view of energy density height, lithium ion battery is noticeable.
Currently marketed lithium ion battery uses the electrolyte containing flammable organic solvent.In the feelings using electrolyte
Under condition, need the safety device that temperature when installing for suppressing short circuit rises and it needs to carry out the structure for preventing short circuit
With the improvement in terms of material.
In contrast, and known be to make the complete solid of battery total solids by solid electrolyte layer alternative electrolyte
Build lithium ion battery.Fully solid lithium ion battery is not owing to using flammable organic solvent in battery, thus liquid
Leakage, danger on fire are less, can be with the simplification of therefore safe device.Therefore, from the reduction of manufacturing cost, safety and can
From the point of view of property, carry out the exploitation of fully solid lithium ion battery.Such as, it is proposed that use non-flame properties solid electricity
Xie Zhi, and the all-solid-state battery that all of the foundation elements is all constituted with solid.
It addition, also disclose a kind of electrode layer containing electrode active material by stacking and solid electrolyte layer and carry out
Burn till, to manufacture the method (referring for example to patent documentation 1) of all-solid-state battery.Further, it may have following example: it makes negative pole
Become sheet, and in sheet negative pole containing fibrous carbon material as conductive agent, and use thermoplastic resin as viscous
Knot agent, thus a kind of high performance all-solid-state lithium-ion battery (referring for example to patent documentation 2) is provided.
On the other hand, as other form of fully solid battery, in recent years, disclose a kind of manufacture to be made up of quasiconductor
The method of charge storage element, described charge storage element is to use electrode from sandwich by the burning covered with Ins. ulative material
Thing semiconductive particles constitute electric power storage layer and p-type semiconductor layer and constitute (referring for example to patent documentation 3, patent documentation 4).Store
Electric layer captures electronics by energy level in the band gap being formed at metal-oxide semiconductor (MOS) microgranule and is charged, and catches by making
The electronics obtained is released and is discharged.As this metal-oxide semiconductor (MOS), titanium oxide (TiO can be listed2), stannum oxide
(SnO2), zinc oxide (ZnO) as an example.This illustration is owing to need not dielectric substrate, and makes by metal-oxide semiconductor (MOS)
The electric power storage layer coating film forming constituted with Ins. ulative material, thus be excellent maximizing, becoming present aspect.Furthermore, from high-energy
From the point of view of density and fully solid battery, it is desirable to the safety advantage such as excellent high, environment resistant.
It addition, in patent documentation 5, it is proposed that and use non-flame properties solid electrolyte to make all of the foundation elements by solid
The manufacture method of the all-solid-state battery that body is constituted.The composition of the all-solid-state battery disclosed in patent documentation 5 possess containing nickel oxide,
The positive pole of nickel hydroxide, lead oxide and lead sulfate etc., solid electrolyte and the negative pole being made up of titanium oxide.By from positive pole
Release proton to solid electrolyte, negative pole is drawn proton from solid electrolyte and is charged, and by back reaction during charging
And discharge.Owing to being formed, there is the solid electrolyte film of porous structure, thus pore surface covered by OH base, by
Water is kept to become solid electrolyte in hole.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2007-5279 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-146581 publication
Patent documentation 3: International Publication the 2012/046325th
Patent documentation 4: International Publication the 2013/065093rd
Patent documentation 5: Japanese Unexamined Patent Publication 2015-082445 publication
Summary of the invention
Invent problem to be solved
The present invention provides a kind of charge storage element making capacity be improved.Furthermore, the present invention also provides for this electric power storage unit a kind of
The manufacture method of part.
For solving the means of problem
The charge storage element of the present invention have the negative electrode collector of electric conductivity, the positive electrode collector of electric conductivity, be arranged in described
Between negative electrode collector and described positive electrode collector and containing Ins. ulative material and the negative pole of mixture of cerium oxide, Yi Jipei
Put the positive pole between described positive electrode collector and described negative pole.
The effect of invention
The present invention can provide the charge storage element and manufacture method thereof making capacity be improved.
Accompanying drawing explanation
Fig. 1 is the schematic sectional view of the charge storage element of embodiment 1.
Fig. 2 is the schematic sectional view of the composition of the negative pole of the charge storage element representing embodiment 1.
Fig. 3 is the process chart of the manufacture method of the charge storage element for embodiment 1 is described.
Fig. 4 is the schematic sectional view of the charge storage element of embodiment 1.
Fig. 5 is the schematic sectional view of the variation of the charge storage element of embodiment 1.
Fig. 6 is the schematic sectional view of other variation of the charge storage element of embodiment 1.
Symbol description:
10,20 charge storage element 11,21 substrate
12 negative electrode collector 13,22 negative poles
14,23 positive pole 15,24 positive electrode collector
16 metal-oxide 17 Ins. ulative material
50 solid electrolytes
Detailed description of the invention
(becoming the viewpoint on present invention basis)
In all-solid-state battery, in order to realize the high performance of battery, it is necessary at room temperature show high connductivity
The exploitation of the solid electrolyte of rate, positive pole and negative material.Further, since there is good electrode-electric solution matter solid interface
The problem such as construct, thus be difficult to stably realize high capacity.It addition, under the effect of charge and discharge cycles, tend to make electricity
Pond deterioration in characteristics.Furthermore, when making these materials, owing to needs carry out long heat treatment under high temperature, thus there is material
The variation of material, it is difficult to make high performance battery.
The present inventor etc. have carried out research with great concentration, found that: by using containing Ins. ulative material and cerium oxide
The negative pole of mixture, it is possible to obtain just can realizing cost degradation and stable action and high power capacity with easy composition
Charge storage element and manufacture method.In other words, find as the negative pole constituting charge storage element, by using containing insulating properties
The material of the mixture of material and cerium oxide, it is possible to obtain the charge storage element of high power capacity.
The charge storage element of one aspect of the present invention have the negative electrode collector of electric conductivity, the positive electrode collector of electric conductivity,
The mixture being arranged between described negative electrode collector and described positive electrode collector and contain Ins. ulative material and cerium oxide
Negative pole and be arranged in the positive pole between described positive electrode collector and described negative pole.
Negative electrode collector plays a role as the 1st electrode, and positive electrode collector plays a role as the 2nd electrode.It addition, negative pole
Play a role as electric power storage layer.It is to say, negative pole is for accumulated charge.
Described cerium oxide can also be microgranule.It addition, described negative pole can also make described microgranule be scattered in described insulation
In property material.The size of described microgranule can also be 1nm～20nm.The mean diameter of described microgranule both can be 1nm～
100nm, it is also possible to for 1nm～20nm, it is also possible to for 1nm～10nm.
Described mean diameter is the value using ultramicroscope to record.In this manual, the burning such as cerium oxide
The mean diameter of the particle of thing uses following method to calculate.First, use ultramicroscope (SEM or TEM) to metal oxygen
The particle of compound is observed.For any 50 primary particles in the image that obtained by this observation (hereinafter referred to as
Particle), calculate the particle diameter a of each particle.The particle diameter a of each particle is the area S obtaining this particle based on described image,
And calculate according to below formula.Then, the meansigma methods of the particle diameter a of described 50 particles is calculated.By this mean value definition
Mean diameter for metal-oxide.
A=2 × (S/3.14)1/2
Described negative pole can also have porous structure.Solid electricity can also be configured between described negative pole and described positive pole
Xie Zhi.Described negative pole can also directly contact to substitute the configuration of solid electrolyte with described positive pole.In the case, insulating properties
Material plays a role as solid electrolyte.
Described negative electrode collector or described positive electrode collector can also be selected from copper, chromium, nickel, titanium, platinum, gold, aluminum, tungsten,
At least one metal among ferrum and molybdenum or the alloy of a combination thereof.
Described charge storage element can also have the phase contacting and being arranged in described negative pole with described negative electrode collector further
The substrate tossed about.Described substrate can also be flexible insulating properties sheet material.Described negative electrode collector can also be also used as substrate.
Described positive pole can also be nickel oxide or copper aluminum oxide.Described positive pole can also be p-type semiconductor.
Described Ins. ulative material can also have selected from silicon organic compound, silicon dioxide, magnesium oxide, aluminium oxide, mineral
At least one among oil.Described Ins. ulative material can also be silicon organic compound.Described Ins. ulative material can also have choosing
From polyethylene, polypropylene, polystyrene, polybutadiene, polrvinyl chloride, polymethyl methacrylate, polyamide, Merlon,
The thermoplastic resin such as polyimides, cellulose acetate and phenolic resin, amino resins, unsaturated polyester resin, pi-allyl tree
At least one among fat, alkyd resin, epoxy resin, polyurethane.
One aspect of the present invention relates to the manufacture method of a kind of charge storage element, comprising: prepare negative electrode collector；Pass through
The microgranule and the Ins. ulative material that make cerium oxide are dissolved in organic solvent and make coating fluid, are coated with on described negative electrode collector
Coating fluid described in cloth and form coated film, and described coated film is burnt till, thus forms negative pole；Described negative pole is formed
Positive pole；And on described positive pole, form positive electrode collector.
Negative electrode collector plays a role as the 1st electrode, and positive electrode collector plays a role as the 2nd electrode.It addition, negative pole
Play a role as electric power storage layer.It is to say, negative pole is for accumulated charge.
At a temperature of 200 DEG C～500 DEG C, described coated film can also be burnt till, thus form described insulating properties material
The microgranule of the described cerium oxide in the matrix expected and the matrix being scattered in this Ins. ulative material.
As described positive pole, it is also possible to form nickel oxide or copper aluminum oxide.Described positive pole can also be that p-type is partly led
Body.
About the mode of charge storage element and manufacture method thereof in order to implement the present invention, carry out detailed underneath with accompanying drawing
Explanation.
(embodiment 1)
The charge storage element 10 of embodiment 1 is as it is shown in figure 1, have the negative electrode collector 12 of electric conductivity, negative pole 13, positive pole
14 and the positive electrode collector 15 of electric conductivity.It addition, in FIG, negative electrode collector 12 is formed on substrate 11.In electric power storage unit
In part 10, the positive electrode collector 15 of the negative electrode collector 12 of electric conductivity, negative pole 13, positive pole 14 and electric conductivity is according to this order stacking
And configure.Here, so-called " configuring according to this order stacking ", including in the way of overturning by lamination order, i.e. with electric conductivity just
Electrode current collector 15, positive pole 14, negative pole 13, the situation of order stacking of negative electrode collector 12 of electric conductivity.In addition it is also possible to allow use
In realizing the intermediate layer of suitable, desired function between each layer.As intermediate layer, such as, may be constructed to prevent from being derived from
The impurity of collector body is diffused as preventing diffusion layer and making electronics effectively move to negative pole or positive pole from collector body of purpose
Electron injecting layer etc..In addition it is also possible to configure solid electrolyte 50 between negative pole 13 and positive pole 14 and constitute charge storage element 10
(with reference to Fig. 5).Such as, solid electrolyte 50 can be with the silicon oxide (SiO that thickness is 5nm2) constitute.
The complex that negative pole 13 is metal-oxide and Ins. ulative material mixes.Negative pole 13 can also be thin film.Gold
Belong to oxide and contain cerium oxide.Cerium oxide is typically n-type semiconductor.In the present embodiment, cerium oxide is for example,
CeO2.But, as long as negative pole 13 plays charging/discharging function, the oxidation number of cerium does not the most limit.It addition, cerium oxide the most not office
It is limited to that there is stoichiometric composition.It addition, negative pole 13 is as in figure 2 it is shown, preferably substantially evenly disperse in Ins. ulative material 17
The microgranule of metal-oxide 16.Microgranule be preferably sized to 1nm～20nm.More preferably below 6nm.Furthermore, negative pole 13 is excellent
Choosing has porous structure, preferably easily keeps water by being present in the OH base of pore surface.By negative pole 13 is set as
Porous structure, and make pore surface have OH base and in hole, keep water, just can improve the migration of ion.
As the example of the thickness of negative pole 13, for 50nm～10 μm.It is preferably 100nm～5 μm, more preferably
200nm～2 μm.
As the material of positive pole 14, for example, transition metal oxide.As the example of transition metal oxide, there is nickel oxygen
Compound (NiO) or copper aluminum oxide (CuAlO2).It addition, as the material of positive pole 14, it is preferably ratio and negative pole 13 contains
Metal-oxide 16 is easier to the material being reduced.
The substrate 11 of the charge storage element 10 constituting present embodiment both can be the material of insulating properties, it is also possible to be electric conductivity
Material.Substrate 11 both can be upright and outspoken, it is also possible to is flexible.As substrate 11, it is possible to use flexible sheet material.?
In the case of this, charge storage element 10 can be used as curvature portion, or be also used as can the purposes of bending.For substrate
11, when being formed on the layer of inorganic matter or organic layer, substrate self is advisable changing.As substrate
The example of 11, such as, can use glass, plastics, macromolecule membrane, silicon substrate, metallic plate, metallic foil sheets and by them
The material being laminated.As substrate 11, can obtain as commercially available material, or known method system can be used
Make.
As long as the negative electrode collector 12 and the positive electrode collector 15 that constitute the charge storage element 10 of present embodiment have conduction
Property.Negative electrode collector 12, the material for example, metal of positive electrode collector 15.As metal, it is possible to use containing selected from copper
(Cu), among chromium (Cr), nickel (Ni), titanium (Ti), platinum (Pt), gold (Au), aluminum (Al), tungsten (W), ferrum (Fe) and molybdenum (Mo) extremely
The metal of few a kind of metallic element or the alloy etc. of a combination thereof.
It addition, as the negative electrode collector 12 of electric conductivity and positive electrode collector 15, it is possible to use transparent collector body.
As transparent electric conductivity collector body, it is possible to use indium-tin-oxide (ITO), indium-zinc oxide (IZO), fluorine-doped tin oxide
(FTO), antimony-doped tin oxide (ATO), Indium sesquioxide. (In2O3), stannum oxide (SnO2), the conducting film such as ZnO containing Al.Additionally, should
Transparent electric conductivity collector body is not limited thereto.
As long as it addition, do not make in the range of the performance reduction of charge storage element 10, it is also possible to by multilayer laminated above-mentioned metal
Or transparent conductive film and the stacked film that constitutes is used as collector body.
As Ins. ulative material 17, it is however preferred to have the Ins. ulative material of thermostability, inorganic insulation material can be listed
Material and insulative resin etc..Such as, as inorganic insulation material, it is possible to use silicon organic compound, silicon dioxide (SiO2)、
Magnesium oxide (MgO), aluminium oxide (Al2O3), mineral oil etc..It addition, as insulative resin, it is also possible to be polyethylene, polypropylene,
Polystyrene, polybutadiene, polrvinyl chloride, polymethyl methacrylate, polyamide, Merlon, polyimides, acetate fiber
Element etc. thermoplastic resin, phenolic resin, amino resins, unsaturated polyester resin, allyl resin, alkyd resin, epoxy resin,
The thermosetting resins etc. such as polyurethane.Wherein, particularly preferably silicon organic compound.
In the case of being configured between negative pole 13 and positive pole 14 by solid electrolyte, only constitute the material of solid electrolyte
If becoming the material of solid acid or solid base etc, then can use.As the material of composition solid electrolyte, such as
It is preferably the inorganic oxygen such as silicon oxide, tantalum oxide, tungsten oxide, niobium oxide, zirconium oxide, hafnium oxide, aluminium oxide, magnesium oxide, zinc oxide
Compound, among them, more preferably silicon oxide.Furthermore, solid electrolyte preferably has porous structure.Thus, logical
Cross and be present in the OH base of pore surface and become easily to keep water, as a result, it is possible to improve the migration of ion.Additionally, it is possible to
To use the macromolecular material with insulating properties to replace the above-mentioned oxide with insulating properties.
The electric power storage principle of the charge storage element 10 of present embodiment may not be clear and definite, but can be presumed as follows.
Power supply (not shown) is connected between negative electrode collector 12 and positive electrode collector 15, applies to negative electrode collector 12
Negative voltage, applies positive voltage to positive electrode collector 15.Thus it is possible to think electronics via negative electrode collector 12 to constitute negative pole
The metal-oxide 16 of 13 supplies, and the ion with positive charge is supplied by positive pole 14, thus metal-oxide 16 is reduced,
Positive pole 14 is oxidized.Common Ins. ulative material 17 can select so that it is is non-conductor relative to electronics, and relative to from
Son is good conductor.More specifically, Ins. ulative material 17 selects proton (H+) and hydroxide ion (OH-) can move freely
Material.Even if it is therefore contemplated that release the applying of voltage, the electronics moved to metal-oxide 16 is also by Ins. ulative material
17 shieldings, thus the redox state of metal-oxide 16 and positive pole 14 is maintained.It is to say, be in charging shape
State, has the function as charge storage element 10.
On the other hand, it is believed that carry out discharging load being connected with negative electrode collector 12 and positive electrode collector 15
In the case of, produce the reaction contrary with above-mentioned charging and return to the state at initial stage.That is, it is believed that from being reduced
Metal-oxide 16 supply electronics via negative electrode collector 12, and to positive pole 14 supply, there is the ion of positive charge, from
And the metal-oxide 16 that is reduced is oxidized, and positive pole 14 is reduced.This state is the output state of energy, belongs to electric discharge shape
State.
It is believed that the hydroxyl that the surface of each particle at metal-oxide 16 within negative pole and interparticle interface exist
Base (OH yl) makes the ionic conductivity of negative pole be improved.
As indicated above, it is believed that by constituting metal-oxide 16 and the institute of positive pole 14 of negative pole 13
Call electrochemical redox reaction and play the function as charge storage element 10.This phenomenon can be repeated.
Underneath with Fig. 3, the manufacture method with regard to the charge storage element 10 shown in Fig. 1 illustrates.Fig. 3 is to manufacture charge storage element
Flow chart.
(operation A)
On the substrate 11, sputtering method etc. is used to form the negative electrode collector 12 of electric conductivity.Additionally, be electric conductivity at substrate 11
Material and in the case of doubling as negative electrode collector 12, operation A can also be omitted.In the case, as shown in Figure 6, can obtain
There is the charge storage element 10 of the positive electrode collector 15 of substrate 11, negative pole 13, positive pole 14 and electric conductivity.
The negative electrode collector 12 of electric conductivity can use the film forming method such as chemical deposition, physical deposition methods to carry out shape
Become.As physical deposition methods, it is possible to use sputtering method, vacuum evaporation, ion plating, pulsed laser irradiation is sunk on target
Long-pending PLD method etc..As chemical deposition, it is possible to use chemical vapour deposition techniques such as plasma CVD, hot CVD, laser CVDs
(CVD), the liquid phase membrane formation process such as wet type plating method such as plating, immersion plating, chemical plating, sol-gel process, MOD method, spray-wall interaction
Method, uses the printing technologies such as the doctor blade method of particle dispersion liquid, method of spin coating, ink-jet method, silk screen print method.Preferably employ sputtering
Any one among method, vacuum evaporation, PLD method, CVD makes.But, it is not limited to these methods.
(process B)
In process B, make the basic coating fluid becoming negative pole 13.As coating fluid, it is possible to use organic acid metal
Saline solution or nanoparticle dispersion liquid.Organic acid metal saline solution is such as by by metal salts of organic acids (slaine of organic acid)
It is dissolved in solvent with Ins. ulative material and makes.Nanoparticle dispersion liquid is by by the particle of metal-oxide, insulation
Property material and solvent mixing and make.
Nanoparticle dispersion liquid uses particle shape metal-oxide.Specifically, by the particle of mixing cerium oxide, absolutely
Edge material and solvent, can mix the nanoparticle dispersion liquid as coating fluid.The grain of the particle of metal-oxide 16
Footpath both can be below 100nm, it is also possible to be below 10nm.The particle diameter of the particle of metal-oxide 16 can also be 20nm with
Under.Particle diameter is the least, and the surface area of per unit volume more improves, thus the most favourable to the high capacity of charge storage element 10.It addition, be
Improve the dispersibility in Ins. ulative material and solvent, it is also possible to implement particle shape metal-oxide to use dispersant or
The pre-treatment of person's surfactant or pretreatment.As dispersant, it is possible to use silane coupler etc..Dispersant does not limit to
In silane coupler, as long as not making the characteristic of charge storage element 10 substantially deteriorate, it is possible to use other material.Metal-oxide 16
The particle diameter of particle can also be more than 1nm.
Metal salts of organic acids can use at least one among aliphatic acid slaine and aromatic acid slaine
Metal salts of organic acids.As metal salts of organic acids, it is possible to use by irradiation ultraviolet radiation in an oxidizing atmosphere or burn till and
Make it decompose or burn such that it is able to being changing into the material of metal-oxide.It is for instance possible to use following method carrys out shape
Become.First, aliphatic acid slaine and Ins. ulative material are dissolved in organic solvent prepare coating fluid.Secondly, such as exist
It is coated with described coating fluid on negative electrode collector and forms coated film.Furthermore, described coated film is burnt till, and irradiates ultraviolet
Line.Aliphatic acid slaine the most used herein above be by this dissolving, be coated with, burn till, ultraviolet irradiates and permissible
It is changed to the material of metal-oxide.As aliphatic acid, such as, can use aliphatic monocarboxylic acid, aliphatic dicarboxylic acid, fat
The aliphatic polycarboxylic acids such as fat race tricarboxylic acids, aliphatic tetrabasic carboxylic acid.
More specifically, as aliphatic monocarboxylic acid, it is possible to use formic acid, acetic acid, propanoic acid, caproic acid, enanthic acid, caproic acid, nonyl
Acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, stearic acid, butenoic acid .beta.-methylacrylic acid, iso-crotonic acid, linolenic acid, oleic acid etc..
It addition, aliphatic acid slaine according to easily decomposed by heating or burning, solvent solubility is high, decompose or
The reasons such as the operation fine and close, easy of the film after burning and cheap and metal salt are readily synthesized, it is however preferred to have straight-chain alkyl
Aliphatic acid and the salt of metal.Such as, 2 ethyl hexanoic acid etc. have the carboxylic acid of branched alkyl at room temperature for aqueous, relative to molten
The dissolubility of agent is the highest, thus is general, if but using and have branched alkyl with such 2 ethyl hexanoic acid as representative
Carboxylate, then when burning till, coated film is easily shunk, thus easily cracks.Furthermore, the shortcoming that also film density is relatively low, and
It is difficult to obtain uniform membrane property.Therefore, in carboxylic acid, compared with the carboxylic acid bigger with the volume using side chain, tool is preferably used
There is the carboxylic acid of straight-chain alkyl.
As aromatic carboxylic acid, it is possible to use aromatic monocarboxylate and aromatic multi-carboxy acid.As aromatic multi-carboxy acid,
Aromatic dicarboxylic acid, aromatic tricarboxylic acids, aromatic tetracarboxylic acid and their mixture etc. can be used.As aromatic series
Monocarboxylic acid, it is possible to use benzoic acid, salicylic acid, cinnamic acid, gallic acid, their mixture etc..As aromatic dicarboxylic acid,
Phthalic acid, M-phthalic acid, p-phthalic acid, their mixture etc. can be used.As aromatic tricarboxylic acids, permissible
Use trimellitic acid etc..As aromatic tetracarboxylic acid, it is possible to use Pyromellitic Acid etc..As aromatic series hexacarboxylic acid, can make
With mellic acid etc..Both can be used alone the slaine of these aromatic acids, it is possible to use multiple aromatic acid slaine
Mixture.
As solvent, it can be the material that dissolves the most fully of the aliphatic acid slaine used.Example as solvent
Son, preferably hydrocarbon system solvent, alcohol series solvent, ester series solvent, ether series solvent and ketone series solvent etc..It is, for example possible to use ethanol,
Dimethylbenzene, toluene, butanol, acetylacetone,2,4-pentanedione, ethyl acetoacetate, methyl acetoacetate etc..
It addition, in operation A and B, both can be that any one is first carried out, it is also possible to parallel.
(operation C)
Then, use method of spin coating etc. by coating solution on negative electrode collector 12, thus form coated film.Example
As, in the case of using method of spin coating to form coated film, make substrate 11 rotate, while using spinner
(spinner) by coating fluid rotary coating on the substrate 11 being formed with negative electrode collector 12.By the rotation of substrate 11, just shape
Become the thin layer of 0.3～3 μm.
Film build method as coating fluid, it is possible to use method of spin coating, the tape casting (casting method), take a picture recessed
Format rubbing method, stick coating method, rolling method, bar rubbing method, dip coating, slot coated method, capillary tube rubbing method, spraying process, spray
Rubbing method, woodburytype, silk screen print method, flexographic printing method (the flexographic printing such as mouth rubbing method
Method), the various methods such as print process such as lithography, reversal printing method, ink-jet method.
(step D)
Then, the negative electrode collector 12 that will be formed with coated film is placed about 10 minutes in the atmosphere of 50 DEG C and is made it do
Dry.Additionally, in the case of the volatility of coating fluid is higher, step D can also be omitted.
(operation E)
Then, burn till at a temperature of 200 DEG C～500 DEG C 10 minutes～about 1 hour.By burning till, just form insulation
Property the matrix of the material 17 and particulate layer of metal-oxide 16 that is scattered in the matrix of Ins. ulative material 17.
(operation F)
Then, to have passed through step D, the coated film of E carries out ultraviolet irradiation.Ultraviolet irradiate such as wavelength 254nm,
Intensity 100mW/cm2Lower irradiation about 30～240 minutes.Additionally, at the organic acid metal that can be made coated film by operation E
In the case of salt, Ins. ulative material decompose fully and burn till, operation F can also be omitted.
As the method carrying out ultraviolet irradiation, it is possible to use high-pressure mercury-vapor lamp, low pressure mercury lamp, YAG laser etc., shine
It is preferred from the point of view of penetrating the energy density high technique productive temp time (tact time) in time can shortening production
's.
It addition, by making above-mentioned step D, the operation of E, F is repeatedly repeated, it is also possible to suitably adjust the film of negative pole 13
Thick.
(operation G)
Then, sputtering method etc. is used to form positive pole 14 in the way of overlapping on negative pole 13.Positive pole 14 can use chemistry
The film forming method such as sedimentation, physical deposition methods is formed.As physical deposition methods, it is possible to use sputtering method, vacuum evaporation,
Ion plating, pulsed laser irradiation is carried out on target the PLD method etc. that deposits.As chemical deposition, it is possible to use plasma
The chemical vapour deposition techniques (CVD) such as CVD, hot CVD, laser CVD, the liquid phase film forming such as wet type plating method such as plating, immersion plating, chemical plating
Method, sol-gel process, MOD method, spray heating decomposition, use the doctor blade method of particle dispersion liquid, method of spin coating, ink-jet method, silk
The printing technologies such as net print process.Preferably employ any one among sputtering method, vacuum evaporation, PLD method, CVD to make.But
It is, it is not limited to these methods.
(step H)
Finally, the positive electrode collector 15 of electric conductivity is formed.The forming method of positive electrode collector 15 and negative electrode collector 12
Forming method (operation A) is same.By above operation, just form charge storage element 10.
Additionally, in the case of solid electrolyte is formed between negative pole 13 and positive pole 14, can then operation F, enter
The operation that row is following.Sputtering method etc. is used to form solid electrolyte in the way of overlapping on negative pole 13.Solid electrolyte is permissible
The film forming method such as chemical deposition, physical deposition methods is used to be formed.As physical deposition methods, it is possible to use sputtering method,
Vacuum evaporation, ion plating, pulsed laser irradiation is carried out on target the PLD method etc. that deposits.As chemical deposition, can make
With wet type plating methods etc. such as the chemical vapour deposition techniques (CVD) such as plasma CVD, hot CVD, laser CVD, plating, immersion plating, chemical platings
Liquid phase membrane formation process, sol-gel process, MOD method, spray heating decomposition, use the doctor blade method of particle dispersion liquid, method of spin coating,
The printing technology such as ink-jet method, silk screen print method.Preferably employ any one among sputtering method, vacuum evaporation, PLD method, CVD to carry out
Make.But, it is not limited to these methods.After this operation, use above-mentioned operation G, formed on the solid electrolyte
Positive pole 14.
The shape when the upper surface of the charge storage element 10 being suitable for the present invention is observed it is illustrated in embodiment described later
For the situation of rectangle, but it is not limited to rectangle, it is also possible to be other shapes such as circle, ellipse, hexagon.Furthermore, as
The composition of charge storage element 10, can select according to the shape that the shape etc. of the composition of stacking, folding is used, the difference of purposes
Various shapes, can take the shape that cylindrical shape, square, button-type, coin-shaped or platypelloid type etc. are desired.Additionally,
It is not limited to above-mentioned shape.
It addition, above be just initially formed negative electrode collector 12, the situation that eventually forms positive electrode collector 15 is illustrated.Instead
It, be initially formed positive electrode collector 15, to eventually form the situation of negative electrode collector 12 be that the order of operation is contrary, concrete operation
Process as described above.
(embodiment)
Then, based on embodiment, use Fig. 4 the present invention is specifically described, but the present invention be not exposed to
Under any restriction of embodiment.
[embodiment 1]
Fig. 4 is the schematic sectional view of the composition of the charge storage element 20 representing embodiment 1.
As substrate 21, using size is that 3cm is square, thickness is the stainless steel substrate of 0.5mm, thus produces Fig. 4 institute
The charge storage element 20 shown.Negative electrode collector is not additionally formed and stainless steel substrate is doubled as collector body.
Negative pole 22 is formed by the steps.First, make the particle of cerium oxide be scattered in appropriate ethyl acetate, enter
And mix silicone oil and be stirred, thus mix coating fluid.Spinner (2000rpm, 10sec) is used to be revolved by above-mentioned coating fluid
Turn coating on the base plate (21, under air, use hot plate, be dried 10 minutes at about 50 DEG C.Then, burn at about 500 DEG C
Become 60 minutes, thus form the hybrid films of cerium oxide and Si oxide.Then, hybrid films uses low-pressure mercury light irradiation
Ultraviolet, thus form negative pole 22.Irradiation condition is set as wavelength 254nm, about 80mW/cm2, 120 minutes.
After defining negative pole 22, use high frequency magnetron sputter device, negative pole 22 is screening square for 2cm via size
Shield plate (shadow mask) and form nickel oxide (NiO) that thickness is 300nm as positive pole 23.Use same method, just
On pole 23 stacking thickness be the tungsten (W) of 150nm as positive electrode collector 24, thus produce charge storage element 20.The electric power storage made
The driving area of element 20 is 4cm2。
Charge-discharge characteristic is evaluated by the charge storage element 20 using the present embodiment 1 made as described above.Making
For, in the constant current charge-discharge test that discharge and recharge measures, carrying out the constant voltage charging of 5 minutes with the charging voltage of 2V, then will put
Electricity electric current density is set as 12.5 μ A/cm2, and discharge cut-off voltage is set as 0V, discharge under conditions of 25 DEG C.?
In above-mentioned constant discharge and recharge test, use the 1470E type discharge and recharge test dress that ソ ラ ト ロ Application (Solartron) company produces
Put.The discharge capacity of the charge storage element obtained based on the result that above-mentioned discharge and recharge measures is as shown in table 1, for 144nWh/
cm2。
[comparative example 1]
Use the microgranule of titanium oxide as metal-oxide, in addition, produce electric power storage unit similarly to Example 1
Part.Use method similarly to Example 1, carry out discharge and recharge mensuration.Discharge capacity is as shown in table 1, for 56nWh/cm2, with
Cerium oxide is used to compare, for relatively low discharge capacity as the charge storage element of metal-oxide.
Table 1
| Discharge capacity (nWh/cm2) | |
| Embodiment 1 | 144 |
| Comparative example 1 | 56 |
[embodiment 2]
The ionic conductance of the negative pole shown in embodiment 1 and comparative example 1 is evaluated.Distinguish on a quartz substrate
Make the negative pole shown in embodiment 1 and comparative example 1, negative pole is formed width and is 3mm and there is the interval that distance is 1mm
Oblong-shaped electrode, thus produce ionic conductance evaluation test portion.By this ionic conductance evaluation test portion room temperature,
After placing 1 hour under 50% relative humidity, electrochemical gaging system (Modulab) is used to be determined.Use AC impedance
Method, under conditions of frequency range is the AC bias that 0.1Hz～1MHz, amplitude are 200mV, by impedance spectrum (Nyquist
Figure) calculate the proton conductivity at 25 DEG C.Its result is as shown in table 2.Shown by table 2: as the metal-oxide of negative pole 22, make
The negative pole phase of titanium oxide is used with the negative pole described in the embodiment 1 of cerium oxide and the metal-oxide shown in comparative example 1
Relatively, higher ionic conductance is demonstrated.It is to say, use cerium oxide as the electric power storage of the metal-oxide of negative pole 22
Element has high power capacity, and cell excellent in cycle characteristics, and fast charging and discharging characteristic is the most excellent.
According to embodiments shown above 1, comparative example 1 and the evaluation of the charge storage element of embodiment 2, by using cerium oxygen
Compound is as the metal-oxide of negative pole 22, compared with the former charge storage element using titanium oxide, it is possible to achieve Gao Rong
Quantify.Furthermore, compared with the lithium ion battery using liquid electrolyte, it is provided that the easy composition of a kind of employing just can
Realize the charge storage element of cost degradation and operating stably.
Table 2
The invention is not limited in above-mentioned embodiment and embodiment, at the model of the invention described in claims
In enclosing, various deformation, change can be carried out.Such as, with in each embodiment described in the embodiment that carries out an invention
The corresponding embodiment of technical characteristic, technical characteristic in embodiment be part or all that solve above-mentioned problem,
Or it is to realize part or all of the effect above, suitable replacement and combination can be carried out.It addition, its technical characteristic is only
Illustrate without in the way of technical characteristic necessary in this specification, it is possible to carry out suitable deletion.
Industrial applicability
As in detail above narration as, the charge storage element of the present invention can provide employing easy composition just can be real
Show cost degradation and stable action and the charge storage element of high power capacity and manufacture method thereof.
Claims (20)
1. a charge storage element, it possesses:
The negative electrode collector of electric conductivity,
The positive electrode collector of electric conductivity,
It is arranged between described negative electrode collector and described positive electrode collector and containing Ins. ulative material and the mixing of cerium oxide
The negative pole of thing, and
It is arranged in the positive pole between described positive electrode collector and described negative pole.
Charge storage element the most according to claim 1, wherein,
Described cerium oxide is microgranule,
Described negative pole is dispersed with described microgranule in described Ins. ulative material.
Charge storage element the most according to claim 2, wherein, the particle diameter of described microgranule is 1nm～100nm.
Charge storage element the most according to claim 2, wherein, the particle diameter of described microgranule is 1nm～20nm.
Charge storage element the most according to claim 2, wherein, the particle diameter of described microgranule is 1nm～10nm.
Charge storage element the most according to claim 1, wherein, described negative pole has porous structure.
Charge storage element the most according to claim 1, wherein, is configured with solid electrolytic between described negative pole and described positive pole
Matter.
Charge storage element the most according to claim 1, wherein, described negative electrode collector or described positive electrode collector are to be selected from
At least one metal among copper, chromium, nickel, titanium, platinum, gold, aluminum, tungsten, ferrum and molybdenum or the alloy of a combination thereof.
Charge storage element the most according to claim 1, wherein, has further and contacts with described negative electrode collector and be configured at
The substrate of the opposition side of described negative pole.
Charge storage element the most according to claim 9, wherein, described substrate is flexible insulating properties sheet material.
11. charge storage elements according to claim 1, wherein, described negative electrode collector is also used as substrate.
12. charge storage elements according to claim 1, wherein, described the most extremely nickel oxide or copper aluminum oxide.
13. charge storage elements according to claim 1, wherein, described Ins. ulative material have selected from silicon organic compound, two
At least one among silicon oxide, magnesium oxide, aluminium oxide, mineral oil.
14. charge storage elements according to claim 13, wherein, described Ins. ulative material is silicon organic compound.
15. charge storage elements according to claim 1, wherein, described Ins. ulative material have selected from polyethylene, polypropylene,
Polystyrene, polybutadiene, polrvinyl chloride, polymethyl methacrylate, polyamide, Merlon, polyimides, acetate fiber
Thermoplastic resin and phenolic resin, amino resins, unsaturated polyester resin, allyl resin, alkyd resin, the epoxies such as element
At least one among resin, polyurethane.
16. according to the charge storage element according to any one of claim 1～15, wherein, described the most extremely p-type semiconductor.
The manufacture method of 17. 1 kinds of charge storage elements, comprising:
Prepare negative electrode collector；
It is dissolved in organic solvent by the microgranule and Ins. ulative material making cerium oxide and makes coating fluid,
Described negative electrode collector is coated with described coating fluid and forms coated film,
And described coated film is burnt till, thus form negative pole；
Described negative pole is formed positive pole；And
Described positive pole is formed positive electrode collector.
The manufacture method of 18. charge storage elements according to claim 17, wherein, to institute at a temperature of 200 DEG C～500 DEG C
State coated film to burn till, thus in forming the matrix of described Ins. ulative material and being scattered in the matrix of this Ins. ulative material
The microgranule of described cerium oxide.
The manufacture method of 19. charge storage elements according to claim 17, wherein, forms nickel oxide or copper aluminum oxide
As described positive pole.
20. according to the manufacture method of the charge storage element according to any one of claim 17～19, wherein, described the most extremely p-type
Quasiconductor.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-029393 | 2015-02-18 | ||
| JP2015029393 | 2015-02-18 | ||
| JP2015-184550 | 2015-09-18 | ||
| JP2015184550 | 2015-09-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105895971A true CN105895971A (en) | 2016-08-24 |
Family
ID=56621607
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610011441.0A Pending CN105895971A (en) | 2015-02-18 | 2016-01-08 | Electrical storage device including anode and cathode |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20160240845A1 (en) |
| JP (1) | JP2017059516A (en) |
| CN (1) | CN105895971A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109643829A (en) * | 2016-08-31 | 2019-04-16 | 日本麦可罗尼克斯股份有限公司 | Secondary cell |
| CN113016087A (en) * | 2018-11-13 | 2021-06-22 | 日本麦可罗尼克斯股份有限公司 | Secondary battery and method for manufacturing same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019140053A (en) * | 2018-02-15 | 2019-08-22 | 株式会社日本マイクロニクス | Secondary battery |
| CN113764616A (en) * | 2018-08-28 | 2021-12-07 | 宁德新能源科技有限公司 | Pole piece and electrochemical device |
-
2015
- 2015-11-11 JP JP2015220988A patent/JP2017059516A/en active Pending
-
2016
- 2016-01-08 CN CN201610011441.0A patent/CN105895971A/en active Pending
- 2016-01-14 US US14/995,856 patent/US20160240845A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109643829A (en) * | 2016-08-31 | 2019-04-16 | 日本麦可罗尼克斯股份有限公司 | Secondary cell |
| CN109643829B (en) * | 2016-08-31 | 2021-12-14 | 日本麦可罗尼克斯股份有限公司 | Secondary battery |
| CN113016087A (en) * | 2018-11-13 | 2021-06-22 | 日本麦可罗尼克斯股份有限公司 | Secondary battery and method for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| US20160240845A1 (en) | 2016-08-18 |
| JP2017059516A (en) | 2017-03-23 |
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